EP0241819B1 - Laminé barrière pour l'emballage d'essences, d'arômes, de l'oxygène et de vitamines et cartons fabriqués à partir des laminés - Google Patents

Laminé barrière pour l'emballage d'essences, d'arômes, de l'oxygène et de vitamines et cartons fabriqués à partir des laminés Download PDF

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Publication number
EP0241819B1
EP0241819B1 EP87104913A EP87104913A EP0241819B1 EP 0241819 B1 EP0241819 B1 EP 0241819B1 EP 87104913 A EP87104913 A EP 87104913A EP 87104913 A EP87104913 A EP 87104913A EP 0241819 B1 EP0241819 B1 EP 0241819B1
Authority
EP
European Patent Office
Prior art keywords
web
laminate
nylon
surlyn
olefin polymer
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP87104913A
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German (de)
English (en)
Other versions
EP0241819A2 (fr
EP0241819A3 (en
Inventor
Kenneth P. Thompson
Richard C. Ihde
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Champion International Corp
Original Assignee
Champion International Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Champion International Corp filed Critical Champion International Corp
Publication of EP0241819A2 publication Critical patent/EP0241819A2/fr
Publication of EP0241819A3 publication Critical patent/EP0241819A3/en
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Publication of EP0241819B1 publication Critical patent/EP0241819B1/fr
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/10—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of paper or cardboard
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2323/00—Polyalkenes
    • B32B2323/04—Polyethylene
    • B32B2323/046—LDPE, i.e. low density polyethylene
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2439/00—Containers; Receptacles

Definitions

  • This invention relates to the barrier laminates for the containment of essential oils, flavors, oxygen and vitamin C and to cartons made therefrom. More particularly, this invention relates to barrier laminates useful in the manufacture of cartons which hold liquids containing essential oils, flavorings and vitamin C such as fruit juices.
  • a laminate providing not only a substantial barrier to the migration of essential oils and/or flavors therethrough but providing for retention of vitamin C is achieved by a laminate comprising from the outer surface to the inner surface in contact with the fruit juice: a paperboard substrate, a web of nylon, a web of Surlyn directly overlying the nylon web and a web of olefin polymer, typically polyethylene directly overlying and in contact with the Surlyn web and rendering the resulting laminate heat sealable.
  • cartons constructed of the laminate of the present invention enable significant essential oil, flavor and vitamin C retention in the fruit juice contained therein resulting in a significant extension of the shelf life of the packaged product and permitting the replacement of the otherwise required aluminium foil barrier at considerable economic savings.
  • the laminate of the invention further provides an effective barrier to the passage of oxygen, thus preserving and protecting vitamins and in particular vitamin C and other nutrients contained in the beverage or juice product from oxidative degradation.
  • this laminate additionally provides an excellent barrier to the migration of essential oils and/or flavors therethrough.
  • one such carton is the gable-top milk carton and carton blanks therefor which are specifically disclosed in US patent 3 120 333 as liquid tight containers.
  • blanks used in the manufacture of such containers include a paperboard base, extrusion coated on both sides with a resin, such as polyethylene, to provide a moisture barrier and to provide means for heat-sealing the carton.
  • the resin on an outer surface of a glue flap and the resin on an inner surface of a carton panel are heated by direct flame application while the heated carton surfaces extend in guided but essentially unsupported, i.e., not compressed between two heating jaws, condition over the edges of a conveying belt.
  • the carton panels are then folded over to form a flattened tube, the now molten tacky resin on the heated surfaces are pressed together at a downstream nip to form a liquid-tight side seam.
  • the cartons, in a flattened tube form are then shipped to users such as dairies or juice manufacturers where they are erected by further heat-sealing, filled and finally sealed.
  • the invention described herein is particularly useful as a paperboard laminate employed in the manu- - facture, for example, of containers of many various types.
  • Such containers may comprise folding boxes, square or rectangular containers or cartons, or simply cylindrical tubes having a bottom closure means and generally also a top closure means.
  • the laminate of the present invention is shown as comprising a paperboard substrate 10 which is most suitably high-grade paperboard stock, for example 0.254-0.710 mm (0.010 to 0.028") milk carton stock onto which is applied a web of nylon 12 in a coating weight range of 2.2 - 6.8 kg per ream (5-15 pounds per ream).
  • a web of nylon 12 in a coating weight range of 2.2 - 6.8 kg per ream (5-15 pounds per ream).
  • Surlyn 13 is DuPont's tradename for the ionomer poly (ethylene-co-methacrylic acid).
  • olefin polymer 14 Overlying and in contact with the Surlyn web is a web of heat sealable olefin polymer 14, preferably polyethylene and most preferably, a low density polyethylene. Typical of the preferred low density polyethylenes which can be employed as web 14 is Gulf 4517 polyethylene available from Gulf Oil Chemicals Company, Houston, Texas. The olefin polymer web 14 is applied in a coating weight ranging from about 1.8 to 9 kg per ream (4 to about 20 pounds per ream).
  • Surlyn AD 8255 is an extrudable terionomer resin (zinc metal salt of an ethylene-based terpolymer) and available in pellet form for use in conventional extrusion equipment designed to process polyethylene resins.
  • Surlyn AD 8255 is characterized by its improved adhesion properties and particularly to nylon.
  • a web of heat sealable olefin polymer 11 typically polyethylene and most preferably low density polyethylene.
  • This external coating of olefin polymer imparts heat sealability to the ultimate container and also imparts a gloss to the external surface of the paperboard which with suitable but conventional treatment can be directly printed on.
  • the paperboard substrate 10 is coated on the external surface thereof with a web of heat-sealable olefin polymer 11, typically polyethylene and most preferably, low density polyethylene.
  • olefin polymer typically polyethylene and most preferably, low density polyethylene.
  • this external coating of olefin polymer imparts heat-sealability to the ultimate container construction and also imparts a gloss to the external surface of the paperboard which can be utilizing conventional techniques directly printed upon.
  • Surlyn 13' Onto the internal surface of the paperboard substrate 10 there is applied a web of Surlyn 13' as described hereinafter.
  • a web 12' of nylon Overlying the Surlyn 13' web and in contact therewith is a web 12' of nylon over which a web 15' of Surlyn has been directly applied. Overlying the web 15' of Surlyn and in contact therewith is a web 14' of heat sealable olefin polymer which will ultimately form the internal surface of the container constructed therefrom.
  • the laminates of the present invention can be easily fabricated.
  • the nylon and Surlyn or the nylon, Surlyn and olefin polymer webs can be directly coextruded onto the paperboard substrate.
  • a layer of Surlyn can be simultaneously coextruded between the paperboard and the nylon webs as they are directly coextruded onto the paperboard substrate.
  • a three- or four-pass coating operation can be employed whereby the nylon polymer web is extruded onto the paperboard substrate and, or subsequently overcoating the nylon barrier web with a web of Surlyn and of olefin polymer.
  • Standard paperboard 1.9 I (1/2 gallon) orange juice containers were prepared and filled with orange juice.
  • the principle essential oil in orange juice is d-limonene.
  • the filled cartons were stored for a period of six weeks after which time the orange juice was analyzed to determine the percentage loss by weight of the essential oil d-limonene and the percentage loss by weight of vitamin C.
  • the standard 1.9 I (1/2 gallon) orange juice container was constructed from a laminate consisting (from the outside of the container in) of 3.5 kg per ream (7.8 pounds per ream) polyethylene, 0.6 mm (0.024") milk carton stock and 9 kg per ream (20 pounds per ream) polyethylene.
  • Another standard paperboard 1.9 I (1/2 gallon) orange juice container was modified to contain an aluminium foil lining.
  • the structure from the outside of the container in was 3.5 kg per ream (7.8 pounds per ream) low density polyethylene, 0.6 mm (0.024”) milk carton stock, 4.5 kg per ream (10 pounds per ream) low density polyethylene, 0.009 mm (.00035”) aluminium foil and 9 kg per ream (20 pounds per ream) low density polyethylene.
  • a third class of comparative standard paperboard 1.9 I (1/2 gallon) orange juice container was prepared from the laminate of US patent 4 513 036 comprising from the outside of the container in 3.5 kg per ream (7.8 pounds per ream) polyethylene, 0.6 mm (0.024") milk carton stock, 4.5 kg per ream (10 pounds per ream) of extrusion coating grade polpropylene and 4.5 kg per ream (10 pounds per ream) low density polyethylene as well as with other coating weights of polypropylene and polyethylene.
  • the experimental cartons were prepared using board coatings which consisted of:
  • the method for determining d-limonene involves a co-distillation of orange juice with isopropyl alcohol, followed by acidification of the distillate and titration with standardized KBr-KBrOs solution.
  • the reaction involves release of bromine, in situ, which then reacts with d-limonene's double bond to form limonene tetrabromide.
  • the ascorbic acid concentration in orange juice was determined by a modified 2,6-dichlorophenol-indophenol titration method.
  • the method involves titrating a sample containing ascorbic acid in the presence of metaphosphoric acid and acetic acid with the dichlorophenol-indophenol standard solution until a distinct pink color persists for 5 seconds.
  • the dichlorophenol-indophenol standard solution is used as a standard oxidizing agent which is colored blue in alkali and red in acid, while the reduced form is colorless.
  • the laminate has incorporated into a suitable intermediate layer particles of a pigment such as aluminium powder or a food grade dye for providing a suitable and more attractive coated product.
  • a pigment such as aluminium powder or a food grade dye for providing a suitable and more attractive coated product.
  • the adhesion characteristics of the film layers are not interfered with and the use of the pigment and/or colorant is applicable to a coextrusion process.
  • the pigmented or colored coated paperboard material comprises a paperboard substrate 10 onto which are coextruded the nylon 12, followed by the Surlyn 13 and the heat sealable olefin polymer 14, with the pigment or colorant incorporated into either the nylon 12 or Surlyn 13 layer and preferably in this construction, into the nylon.
  • the pigment or colorant is incorporated into any of the layers of Surlyn 13' nylon 12' and Surlyn 15'.
  • the pigment or colorant is preferably aluminium particles, but the coated paperboard can be pigmented with any color i.e., white, terra-cotta, blue, yellow, so long as the pigment chosen has sufficient heat resistance to withstand the extrusion conditions.
  • any suitably colored heat resistant pigment can be employed, i.e., animal pigments, synthetic pigments, elemental pigments e.g., carbon black or aluminium powder, inorganic pigments such as inorganic oxides, sulfides, hydroxides, carbonates, silicates, chromates, sulfates, and the like, as well as organic pigments.
  • any certified color i.e., FD & C color permissible for use in foods, drugs or cosmetics may be used if they additionally meet the requirement of compatibility with the extrusion process.
  • the pigment or colorant is incorporated into the intermediate film forming layer i.e., nylon or Surlyn in an amount of from about 1/2 to about 15 weight percent, preferably from 1 to 10 weight percent and more preferably from 1-1/2 to 6 weight percent.
  • the aluminium is preferably used in the form of finely divided aluminium powder and is most conveniently added to the nylon or Surlyn in the form of a blend thereof in the same polymer.
  • Ti0 2 is used as a pigment, it can be used, as is conventional in the plastic industry.
  • the various layers including the intermediate layer containing the pigment are extruded or coextruded onto the paperboard substrate by methods well known in the art.

Landscapes

  • Laminated Bodies (AREA)
  • Cartons (AREA)
  • Wrappers (AREA)

Claims (16)

1. Laminé assurant une barrière à la migration des huiles essentielles et/ou des arômes, ainsi que la rétention de la vitamine C contenue dans les jus de fruits, comprenant, à partir de la surface externe en direction de la surface interne, en contact avec ledit jus de fruit: un substrat de carton (10, 10'), une couche intermédiaire, et un voile de polymère d'oléfine (14, 14') formant la surface interne, caractérisé en ce que la couche intermédiaire comprend au moins un voile de nylon (12, 12') et un voile d'ionomères d'acide poly(éthylène-co-méthacrylique), connu sous la marque de Surlyn (13, 15') reposant directement sur et en contact avec ledit voile de nylon, et caractérisé en ce que le voile de polymère d'oléfine (14, 14') repose directement sur et est en contact avec ledit voile de Surlyn (13,15').
2. Laminé selon la revendication 1, caractérisé en ce qu'il comprend en outre un voile de polymère d'oléfine externe (11, 11') à la surface du substrat de carton (10, 10') à l'opposé de la surface revêtue de voile de nylon (12, 12').
3. Laminé selon la revendication 1 ou 2, caractérisé en ce que la couche intermédiaire comprend en outre un voile de Surlyn additionnel (13') entre le substrat de carton (10') et le voile de nylon (12').
4. Laminé selon l'une des revendications 1 à 3, caractérisé en ce que ledit polymère d'oléfine (14, 14') reposant sur ledit voile de Surlyn (13, 15') est le polyéthylène.
5. Laminé selon la revendication 4, caractérisé en ce que ledit polymère d'oléfine (14, 14') est du polyéthylène basse densité.
6. Laminé selon l'une quelconque des revendications 1 à 5, caractérisé en ce que le substrat de carton (10, 10') est de la pâte de carton à lait standard de 0,25 à 0,710 mm d'épaisseur.
7. Laminé selon l'une quelconque des revendications 1 à 6, caractérisé en ce que ledit voile de polymère d'oléfine externe (11, 11 est du polyéthylène basse densité.
8. Laminé selon l'une quelconque des revendications 1 à 7, caractérisé en ce que ledit voile de nylon (12, 12') est appliqué à un poids de revêtement allant de 2,2 à 6,8 kg par rame.
9. Laminé selon l'une des revendications 1 à 8, caractérisé en ce que ledit voile de polymère d'oléfine (11,11 14, 14') est appliqué à un poids de revêtement allant de 1,8 à 9 kg par rame.
10. Laminé selon l'une quelconque des revendications 1 à 9, caractérisé en ce que l'un desdits voiles de nylon et de Surlyn (12, 12'; 13'; 13,15') contient un pigment ou un colorant de qualité alimentaire.
11. Procédé pour réduire la migration des huiles essentielles et/ou des arômes à partir d'un liquide, et pour y retenir la vitamine C, par utilisation d'un récipient de carton revêtu à l'intérieur de polymère d'oléfine contenant un laminé selon la revendication 1.
12. Procédé selon la revendication 11, caractérisé en ce qu'on interpose un voile additionnel de Surlyn (13') entre ledit voile de nylon (12') et ledit carton (10').
13. Procédé selon la revendication 11 ou 12, caractérisé en ce que l'un desdits voiles de nylon et de Surlyn (12, 12'; 13'; 13, 15') contient un pigment ou un colorant de qualité alimentaire.
14. Procédé selon la revendication 13, caractérisé en ce que ledit pigment est une poudre d'aluminium.
15. Procédé selon l'une quelconque des revendications 11 à 14, caractérisé en ce qu'on applique à la surface externe du carton (10, 10') un revêtement additionnel de polymère d'oléfine (11, 11').
16. Récipient pour liquides contenant des huiles essentielles et/ou des arômes et de la vitamine C construit à partir du laminé de l'une des revendications 1 à 10.
EP87104913A 1986-04-07 1987-04-02 Laminé barrière pour l'emballage d'essences, d'arômes, de l'oxygène et de vitamines et cartons fabriqués à partir des laminés Expired - Lifetime EP0241819B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US84894086A 1986-04-07 1986-04-07
US848940 1986-04-07

Publications (3)

Publication Number Publication Date
EP0241819A2 EP0241819A2 (fr) 1987-10-21
EP0241819A3 EP0241819A3 (en) 1988-10-12
EP0241819B1 true EP0241819B1 (fr) 1990-07-11

Family

ID=25304678

Family Applications (1)

Application Number Title Priority Date Filing Date
EP87104913A Expired - Lifetime EP0241819B1 (fr) 1986-04-07 1987-04-02 Laminé barrière pour l'emballage d'essences, d'arômes, de l'oxygène et de vitamines et cartons fabriqués à partir des laminés

Country Status (10)

Country Link
EP (1) EP0241819B1 (fr)
JP (1) JP2661684B2 (fr)
AU (1) AU600477B2 (fr)
BR (1) BR8701621A (fr)
CA (1) CA1271695A (fr)
DE (1) DE3763618D1 (fr)
DK (1) DK164585C (fr)
FI (1) FI86610C (fr)
IE (1) IE59637B1 (fr)
MX (1) MX168141B (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6383582B1 (en) 1996-07-17 2002-05-07 Enso Oy Laminated package material, method for manufacturing the same, and a package
EP3706998A4 (fr) * 2017-11-10 2021-07-28 Stora Enso Oyj Matériau d'emballage à propriétés barrière

Families Citing this family (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
SE453979B (sv) * 1986-07-04 1988-03-21 Tetra Pak Ab Forpackningslaminat av pappersskikt och plastskikt forsett med ett genom elektronbestralning herdbart fergskikt, laminatets anvendning till behallare samt av laminatet tillverkad behallare
CA2015361A1 (fr) * 1989-05-11 1990-11-11 Donna M. Woodhall Contenant en carton lamine resistant a l'absorption, et flans pour sa construction
JP3007408B2 (ja) * 1990-11-14 2000-02-07 大日本印刷株式会社 バリアー性紙複合容器
JPH0550564A (ja) * 1991-08-21 1993-03-02 Dainippon Printing Co Ltd バリアー性紙複合容器
JPH0550563A (ja) * 1991-08-21 1993-03-02 Dainippon Printing Co Ltd バリアー性紙複合容器
US6149993A (en) * 1991-06-26 2000-11-21 Westvaco Corporation Oxygen and flavor barrier laminate including amorphous nylon
CA2070349C (fr) * 1991-06-26 2002-03-19 Christopher J. Parks Produit d'emballage lamine, incluant du nylon amorphe, offrant une barriere contre la penetration de l'oxygene et la perte des saveurs
DE4212290C2 (de) * 1992-02-29 1996-08-01 Kurz Leonhard Fa Wertdokument
JPH06340037A (ja) * 1993-05-31 1994-12-13 Toppan Printing Co Ltd 耐アルカリ性を有する液体用紙容器
US6964797B2 (en) 1996-07-17 2005-11-15 Stora Enso Oyj Laminated package material, method for manufacturing the same, and a package
JPH1149141A (ja) * 1997-08-01 1999-02-23 Dainippon Printing Co Ltd 紙容器
JP3842247B2 (ja) * 2003-06-25 2006-11-08 大日本印刷株式会社 バリア−性紙容器
FI123071B (fi) 2006-07-28 2012-10-31 Stora Enso Oyj Eteenimetyyliakrylaattikopolymeerin käyttö D-limoneenin imeytymisen pienentämiseen sitrusmehusta
JP7146363B2 (ja) * 2016-09-16 2022-10-04 アサヒ飲料株式会社 容器詰果汁含有飲料

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3972467A (en) * 1974-08-06 1976-08-03 International Paper Company Paper-board laminate
FR2338197A1 (fr) * 1976-01-13 1977-08-12 Durand Jean Nouvelle feuille complexe pour l'emballage des fromages a pate molle
JPS5812867B2 (ja) * 1976-07-31 1983-03-10 積水化学工業株式会社 容器の製造方法
US4423185A (en) * 1980-03-03 1983-12-27 Asahi Kasei Kogyo Kabushiki Kaisha Thermoplastic resinous composition
JPS5874532U (ja) * 1981-11-12 1983-05-20 サンスタ−株式会社 押出しチユ−ブ用積層材
US4513036A (en) * 1983-10-17 1985-04-23 Champion International Corporation Barrier laminates for containment of essential oils and flavors and cartons made therefrom

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6383582B1 (en) 1996-07-17 2002-05-07 Enso Oy Laminated package material, method for manufacturing the same, and a package
EP3706998A4 (fr) * 2017-11-10 2021-07-28 Stora Enso Oyj Matériau d'emballage à propriétés barrière

Also Published As

Publication number Publication date
EP0241819A2 (fr) 1987-10-21
DK164585C (da) 1993-03-15
JP2661684B2 (ja) 1997-10-08
DK164585B (da) 1992-07-20
DE3763618D1 (de) 1990-08-16
IE870884L (en) 1987-10-07
FI871515A0 (fi) 1987-04-07
EP0241819A3 (en) 1988-10-12
FI86610C (fi) 1992-09-25
FI871515A (fi) 1987-10-08
DK173687D0 (da) 1987-04-03
JPS6322642A (ja) 1988-01-30
AU600477B2 (en) 1990-08-16
MX168141B (es) 1993-05-06
BR8701621A (pt) 1988-01-26
IE59637B1 (en) 1994-03-09
CA1271695A (fr) 1990-07-17
DK173687A (da) 1987-10-08
FI86610B (fi) 1992-06-15
AU7093787A (en) 1987-10-08

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